Polymerization of cyclopentadiene



Patented Oct. 3, 1944 UNITED; STATES PATENT OFFICE romiunm'za'rron OF'CYOIDPENTADIENE Samuel G."Trepp, Swarthrnoraflm, assignor to .The'United Gas Improvement Company, a co!- poration oi Pennsylvania 'No Drawing. Application July 22, 1958,

, SerialNo. 220,103

This. invention pertains generally to the catalytic polymerization oi unsaturated coma-,1

pounds such as'cyclopenta'diene and pertains par ticularly tothe use of antimony chloride-organic f solvent complexes and/or: antimony bromide-- v organic solvent complexes as catalysts. .1 :3

The invention willbe described inconnection with the production oicyclope'ntadiene polymer" However, it; is to be understood that it may be employed in the production of a specific type.

of polymers of other types.

e Cyclopentadiene may bepolymerized into at least two broad types .of polymers one of which q is-eharacterized by'being soluble in solvents such as benzene, toluene, chloroform, carbon tetrachloride, and high. flash na htha, while the other is characterized by being vents. e

- The polymerization is usually carried but while the cyclopentadiene isin solution in a solvent.

1 I have discovered that the soluble type of polymer may be produced with antimony chloridee organic solvent complexes and/or antimony w bromide-organic solvent complexes by a careful control of the polymerizing reaction.

Examples of antimony chloride complexes and antimony bromide complexes are antimonyehloride-benzene complex, antimon'y bromide-benzene complex, antimony chloride-toluene complex,

antimony bromide-toluene. complex, antimony chloride-diethyl ether complex, antimony bro-- 'mide-diethyl ether complex, and complexes of antimony chloride or antimony bromide with dialkyl or aryl alkyl ethers generally. r The preparation of complexes oi this character in general comprises adding antimony chloride (SbCh) or antimony bromide (SbBrs), as the case mightbe, to the solvent with agitation.- As a result, if a reaction takes place, a definite chemical compound is formed. I

There are at least four factors which influence production ofsollible polymer. These four factors are (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of uniformly distributed catalyst and (4) time.

Generally;speaking,'and all other conditions remaining the same, it appearsthat there is a threshold temperature for the formation of insoluble polymer. and that at all temperatures itelow' this threshold temperature the soluble polymer results. It is recognized, that'high concentrations'of. cyclopentadiene and/or high proportions of uniformly distributed catalyst might place this theoretical threshold temperature be,-

soluble in these sol-- low commercially obtainable temperature levels. 'However, for reasonable concentrations of cyclopentadiene and-reasonable proportions of uni- .formly distributed catalyst at threshold temperature can be shown to exist for any given concentration of cyclopentadiene with any given proportion. of uniformly distributed catalyst.

7 Also: generally speaking, and all other conditions remaining the same, it appears that there is a threshold concentration of cyclopentadiene for the formation of insoluble polymer, and that at. all concentrations below this threshold concentration the soluble form of polymer results. The term fconcentration of cyciopentadiene as used herein and in the claims specifies. the per- 'centage by weight of total cyclopentadiene,

whether reacted or not, after all of the materials .have'been combined. It is recognized that inordinately high temperatures and/or inordinately high proportions of uniformly distributed catalyst may make the theoretical threshold concentration difficult of determination. However, for

' reasonable temperatures and reasonable proportions of uniformly distributed catalyst a. threshold concentration of cyclopent-adiene can be shown to exist at any given temperature with any given proportion of uniformly distributed catalyst.

Alsogenerally speaking, and all other conditions remaining the same, and assuming that all of the materials have been combined, it appears that there is a threshold proportion of uniformly distributed catalyst for the formation of insoluble polymer, and that with all proportions below this threshold the soluble polymer results.

' In this connection experiments indicate quite "clearly that catalyst is apparently used up during the'polymerization of soluble polymer, and that additional catalyst is required to convert the soluble polymer into insoluble polymer. If the proportion of uniformly distributed catalyst is It is recognized that inordinately high temperatures and/or inordinately high concentrations of cyclopentadiene may make the theoretical.

of 1 uniformly distributed threshold proportion However,- for catalyst diflicult of determination.

reasonable temperatures and reasonable concen trations of cyclopentadiene a threshold proportion of uniformly distributed catalyst can be shown to exist at any given temperature .with any given concentration of cyclopentadiene.

Also generally speaking, and all other conditions remaining the same, it appears that there is a threshold reaction time for the formation of insoluble polymer, and that for all reaction times below this threshold reaction time the soluble polymer results. It is recognized that low temperatures, low concentrations of cyclopentadiene, and/or low proportions of uniformly distributed catalyst may cause this theoretical threshold reaction time to approach infinity. On the other hand, high temperatures, high concentrations of cyclopentadiene and/or high proportions, of uniformly distributed catalyst may cause this theoretical threshold reaction time to approach zero. However, for reasonable temperatures, for reasonable concentrations of cyclopentadiene, and/or for reasonable proportions of uniformly distributed catalyst, a threshold reaction-time can be shown to exist.

Threshold reaction time, however, diiiers from the other three factors in that when the threshold reaction time becomes more than one hour the time necessaryto' form insoluble polymer approaches infinity at a very rapid rate.

When threshold conditions are just exceeded insoluble polymer is formed but not exclusively. This results in a mixture of soluble and insoluble polymer. x

When exceeding threshold conditions to a greater extent, however, insoluble polymer is formed exclusively. The band over which both soluble and insoluble polymers are formed varies in width with change in conditions. For instance this band decreases inwidth with increase in temperature.

Furthermore, the exact values of (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of uniformly distributed catalyst and (4) time at which insoluble polymer begins to appear may vary somewhat with change in purity or source of cyclopentadiene or of catalyst or of solvent or a change in catalyst or solvent. How- ,ever, the exact values may be readily determined by test. r

The soluble polymer obtained varies in physical characteristics with the solvent used during the polymerization. For instance soluble polycyclopentadienes obtained by polymerizing cyclopentadiene by my new process in solvent naphtha, toluene, or benzene differ somewhat fromeach other as shown, for example, in the suitability of these polycyclopentadienes for coating metals for which they are unusually well suited. As an illustration, for certain purposes the benzene polymer is superior, the toluene polymer coming next but being, nevertheless, particularly well suited.

Accordingly, in the preparation of my polymerized cyclopentadiene a solution of cyclopentadiene in a chosen solvent such as toluene is em ployed.

I use as catalyst one or more antimony chloride-organic solvent complexes and/or antimony brom de-organic solvent complexes.

The complex catalysts are preferably employed in the form of suspensions, emulsions, or solutions in organic solvents of which benzene. toluene, solvent naphtha and petroleum naphtha are examples. Such suspensions, emulsions, or solutions are formed by adding the catalyst to the solvent followed by stirring. As an example, I find that a concentration of antimony chloride material to the other is complex in toluene of 15% by weight of toluene is very suitable as a catalyst suspension although any other concentration or solvent suitable for the purpose may be employed. y

The reactants should not be combined too rapidly since under such circumstances the reaction may proceed too violently and cause local overheating with the production of insoluble polymer, or undesirable color bodies, or both, which it is proposed to avoid.

While the catalyst may be added to the solution of cyclopentadiene particularly when the catalyst itself is in solution or in suspension in a solvent, I prefer to add the solution of cyclopentadiene to a suspension, emulsion or solution of the catalyst. This affords a more exact control of the amount and distribution of cyclopentadiene undergoing reaction at any one time. The reaction proceeds much more smoothly than when the catalyst is added to the cyclopentadiene. In the latter case no reaction appears to take place until a certain catalyst concentration is reached whereupon the reaction proceeds at a very high rate, and may get out of control.

In either event, however, the addition of one preferably accompanied by thorough stirring which is preferably rapid to insure uniform distribution not only of the materials but also of temperature.

In addition the reaction is preferably carried out in apparatus capable of temperature control such as a jacketed vessel. provided with an agitator. A very effective control of the temperature of the reaction and of local superheating is afl'orded when the preferred procedure is followed.

As an example, the proportion of catalyst may conveniently be between 40% to 100% by weight of cyclopentadiene provided the temperature of the reaction is controlled and/or the concentration of cyclopentadiene is sufllciently low, thus I avoiding the formation of insoluble polymer.

A proportion of catalyst of by. weight of the total cyclopentadiene present is found to be very convenient. It permits wide variation in temperatures and in concentrations of cyclopentadiene without danger of the formation of insoluble polymer. Furthermore, there is less likelihood of discoloration of the final product than if a larger proportion of catalyst were used.

Incidentally, it appears that the molecular weight of the resulting soluble polycyclopentadienemay be varied somewhat by varying the proportion of catalyst.

For instance, at all temperatures below 50 C.

gel-like polymers are obtained when high proportionsof catalyst are employed just below threshold conditions.- The ease with which gel-like polymers are obtained increases with decrease in temperature. These polymers are completely soluble.

- Incidentally, the formation of gel does not indicate definitely the presence of insoluble polymer as shown above.

Discoloratlon of the product appears to increase and decrease with increase and decrease in proportion of catalyst so that'lower proportions of' catalyst yield materials of lesser discoloration.

Temperatures above C. are preferably avoided and it is recommended that reat care be taken to keep the temperatures throughout the reaction below this point.

It is found that temperatures between 40 C. to 70 are suitable provided the reactants are sufliciently agitated or other steps taken to avoi local overheating. The preferred temperature range is between -40?" C. and 80 C.

Incidentally, it appears that the molecular weight of the resulting soluble polycy'elopentadiene may be varied somewhat by varying the temper ature.

, The increase in color due to increased reaction temperature is quite noticeable at 45 C. and becomes very pronounced asthe reaction tempera-- ture approaches 100 C.

0n the other hand, at 0 C. and even though the proportion. of catalyst' is fairly high, surprisingly light colored polymers are obtained.

howf reaction temperatures are therefore indicated.

Cy'clopentadiene solutions of any suitable con centration can be used, keeping in mind what has been said with respect to threshold conditions, although I more often employ concentrations of cyclopentadiene of. from to by weight oi totalreactants.

Incidentally, it appears that the molecular" about threshold conditions. I find that ior'practicable purposes andgood yields other. conditions should be chosen such that the reaction time is somewhere in the neighborhood of onehour ormore. This is borne out by the'fact that the, yield increases with reaction time up to a certain point; The

to obtain good yields.

The following specific examples will-serve to further illustrate the'invention.

- Example 1 I 81 grams of antimony chloride diethyl ether complex are added to 100 grams of toluene with thorough agitation to form a suspension, emulsion or solution. 4

A mixture of 100 grains of cyclopentadiene and 50 grams oi toluene are added to the suspension during the course of 10 minutes, the temperature ranging from' 12 C. to 15 C. during the addition. The mixture is then agitated for five hours at .15 C., after which 75 grams of a aqueous NaOH solution is added.- This isfollowed by'aai tation for one hour. I

225 grams of quicklime (CaO) are now added to the reaction mixture followed by agitation for an additional hour to dry the mix.

A suitable quantity of a filter aid is then added. and the mixture filtered The filter cake is washed with toluene and the washings added to] I the product.

A solution containing 79 grams of soluble polycyclopentadiene is thus obtained.

Generally speaking, any other antimony chlo- I ride-organic solvent complex or any antimonytime is, of course, preferably chosen) speed and uniformity of-thereabtion and of the amount of heat evolved and consequently-the .'type of polymer produced. The reaction runs smoother and is much more easily controlled on a large scale.

The addition of water to hydrolyze the catalyst makes it possible not only to completely remove the activity of the catalyst and thus stop. the reaction at any point. but also makes it possible to remove the corrosive and discoloring acid constituents of the catalyst by a suitable alkali. The alkali is preferably added with the water used to hydrolyze the catalyst, although it may be added later if desired. The failure to substan-. tially completely remove the catalyst and its hydrolysis products may be the cause of serious discoloration. 'The insoluble reaction products formed during the hydrolysis and neutralization remain behind on the filter leaving a highly purified filtrate.

Erample- 2 27 grams of antimony chloride-benzene complex are added to 150 grams of toluene with thor- I the reaction mixture followed by agitation for 16 p'entadiene is thus obtained.

ough agitation to form a suspension, emulsion or solution.

A mixture of grams of cyclopentadiene and 50 grams of toluene are added to the suspension during the'cours'e of 8 minutes, the temperature ranging from 15 to 25 C. during the addition. The mixture is then agitated for an additional period of5 hours at 15 C. 25 cubic centimeters of an'll% sodium carbonate solution is added; This is followed by agitation for one hour.

50 grams of quicklime (CaO) are now added to hours. Y

' 100 grams of a suitable filter aid are and the mixture filtered.

A solution containing 33 grams of polycyclothen added The polymer may be used as such, or it may be concentrated in a vacuum still of suitable design to give a product containing any desired- It' will be noted that at 'no time did the temperabromide-organic solvent complex might be subare in diluted form before addition. Further-- more, as pointed out above diluted cyclopentadiene is preferably added to diluted catalyst rather a I than vice verse. to aii'ord a better control of the eluding solid polycyclopentadiene, or it might be diluted to give any desired lower concentration, or a second solvent might be substituted such as a higher boiling solvent. This may be done either before'or after concentration by adding the second solvent and distilling.

In the above examples the particular temperatures were chosen to control the physical proD- erties such as viscosity and color of the product.

ture exceed C. or even 70 C. The manner of combining the reactants, constant agitation, and

brine cooling made it possible to prevent local overheating, and the formation of insoluble polymer.

In the above examples (1) temperature; (2 concentration of cyclopentadiene, (3) proportion 'of uniformly distributed catalyst, and (4)v re- .action time may be varied considerably in the production of soluble polymer having in mind what has been said with respect to threshold conditions. If it is foundthat insoluble polymer is obtained, one or more of the four conditions, namely (1) temperature, (2) concentration of cyclopentadiene, (3) proportion of catalyst, and

1(4) reactionltime should be reduced until the soluble polymer is obtained.

Carrying out the polymerization in the presence of a solvent makes it possible to have any desired concentration of cyclopentadiene.

While in the above example no dilution of the product was required to facilitate hydrolysis and/r filtering. it is to be understood that dilution with a solvent may be employed, if desired, particularly in the case of highly viscous products.

Generally speaking, for the formation oi. soluble polymer to the exclusion of insoluble polymer and of extreme discoloration, temperatures should rarely exceed 100 C., and preferably should not exceed 70 0., concentrations of cyclopentadiene should rarely exceed 50% b weight of the total solution except possibly at low temperatures, and concentrations of uniformly distributed catalyst should rarely exceed 100% by weight of cyclopentadiene.

It should be kept in mind that there are for practical purposes minimum values for temperature, concentration of cyclopentadiene, proportion of catalyst and time, which practice will show ought to be exceeded to obtain reasonable yields.

On the other hand, if the maximum values given,

in the previous paragraph for temperature, catalyst and cyclopentadiene' were used simultaneously, insoluble polymer would be formed, even though the reaction time chosen were as short as good practice would permit.

It is by the observance of the preferred principles set forth herein that a quality product is produced in good yield.

While in the above specific examples toluene is used as a polymerization medium, it is to be understood that any other solvent may be substituted of which benzene, xylene, ethyl benzene, solvent naphtha, petroleum naphtha, carbon tetrachloride, decaline, triethylbenzene and ethylene dichloride are especially suitable. The products with benzene and toluene are preferred for specific uses as hereinafter referred to;

While the use of pure cyclopentadiene in solution in a suitable solvent simplifies the system from the standpoint of the number of components present, the invention might be applied to solutions of crude cyclopentadiene in various states Both neutralization and drying is eflected by of purity with various degrees of success depend ing upon the results desired.

Examples of crude cyclopentadiene are the cyclopentadiene containing fractions obtained in the distillation of tar, drip oil and medium and low temperature condensates resulting from subjecting manufactured city gas such as carburetted water gas, oil gas,-or coal gas to refrigeration.

Although in the above particular description both reactants, namely, catalyst and unsaturated compound, are diluted prior to their admixture, it is to be understood that variations are possible. For instance, it is conceivable that all of the diluent may be first mixed with one of the reactants (either catalyst or unsaturated compound) and that the other reactant may be added in concentrated form, particularly if the Drinci pies set forthherein are closely observed. Or the larger part of the diluent may be added to one of the reactants so that the other is relativelyconcentrated. It is also conceivable that. with the exercise of extreme care and the closest adherence ,to the principles set forth herein, both .reactants might possibly be employed in relatively concentrated form. Other variations are possible. When adding one liquid to 'another with agitation l find it convenient and often preferable to do this below the surface of one of the liquids. i

CaO.'

In case it is desired to form a highly concentrated solution of polycyclopentadiene, or to isolate it in solid form, it is not necessary to dry the solution after neutralization as the water present can be readily removed in the subsequent concentrating operation. The complete removal of insoluble material present, such as the neutralizing agent, is then eifected by filtering the partially concentrated solution after the complete removal of the water present by distillation. After this step the solution can be further concentrated if desired.

The product may be used for many purposes,

for instance for lacquers generally, for varnishes either alone or in admixture with other resins, for enamels, for paints, or in fact for coating compositions generally. It is ideally suited to the coating of metals, for instance, for the coating of food containers as described and claimed in copending application, Serial Number 174,011, filed November 11, 1937, by Newcomb K. Chaney. This is especially true of the products polymerized in benzene and toluene.

If desired, it is possible to obtain soluble polycyclopentadiene of higher viscosity or of otherwise changed characteristics by starting with a solution of polycyclopentadiene and stopping the reaction before threshold conditions are exceeded.

It is to be understood that the above specific examples are by way of illustration. Therefore,

changes, omissions, additions, substitutions, andl or modifications might be made within the scope of the claims without departing from the. spirit of the invention which is intended to be limited only as required by the prior'art.

I claim:

1. A process for producing benzene-soluble polycyclopentadiene by the catalytic polymerization of cyclopentadiene in the substantial absence of all other compounds polymerizable under the conditions obtaining, comprising mixing with said cyclopentadiene in the presence of a solvent to effect said polymerization in considerable proportion to polycyclopentadiene one of a group consisting of hydrolyzable antimony chloride-organic solvent complexes and hydrolyzable antimony bromide-organic solvent complexes, said complex being previously formed by reacting the corresponding antimony halide with an organic solvent capable of reacting with said antimony halide to form said hydrolyzable complex; and preventing the polymerization of said cyclopentadiene from being effected entirely to bencyclopentadiene in the presence of a solvent to eflect said polymerization in considerable proportion to'polycyclopentadiene one of a groupv consisting of hydrolyzable antimony chloride-organic solvent complexes and hydrolyzable antimony bromide-organic solvent complexes, said complex being previously formed by reacting the corresponding antimony halide with an organic solvent capable of reacting with said antimony halide to form said hydrolyzable complex; and preventing the polymerization of said cyclopentadiene from being eflected largely to benzeneinsoluble polycyclopentadiene by thoroughly agitating the reaction mass while maintaining the 7 reaction temperature below 45 C., the concentration of said cyclopentadiene below 50% by weight,

and the proportion'of catalyst to said cyclopentadienebetween 40% and 100% by weight, and by stopping the reaction by inactivating said catalyst while benzene-soluble polycyclopentadiene is the preponderant polymer present in the reaction mass.

3. A process for producing benzene-soluble polyeyclopentadiene by the catalytic polymerization oi! cyclopentadiene in the substantial absence of all other compounds polymerizable under the conditions obtaining, comprising mixingwith said cyclopentadiene in the presence of a solvent to efiect said polymerization in considerable proportion to polycyclopentadiene one of a group preventing the polymerization of said cyclopentadiene from being effected entirely to benzeneinsoluble polycyclopentadiene by thoroughly agitating the reaction mass ,while maintaining the reaction temperature between and 30 C.,

the concentration of said cyclopentadiene below by weight, and the proportion of catalyst to said cyclopentadiene below by weight, and

by stopping the reaction by inactivating said catalyst while benzene-soluble polycyclopentadiene is present in the reaction mass.-

SAMUEL G. TREPP. 

